US6413964B1ExpiredUtility

Inhibitors of prenyl-protein transferase

71
Priority: Jan 12, 2000Filed: Jan 9, 2001Granted: Jul 2, 2002
Est. expiryJan 12, 2020(expired)· nominal 20-yr term from priority
A61P 35/00A61P 9/04C07D 515/08A61P 13/12
71
PatentIndex Score
6
Cited by
26
References
18
Claims

Abstract

The present invention is directed to peptidomimetic macrocyclic compounds of the formula A:wherein W is a heterocycle, V is a heterocycle or aryl moiety and Z1 is a suitably substituted aryl or heterocycle moiety. The instant compounds inhibit prenyl-protein transferase and the prenylation of the oncogene protein Ras. The invention is further directed to chemotherapeutic compositions containing the compounds of this invention and methods for inhibiting prenyl-protein transferase and the prenylation of the oncogene protein Ras.

Claims

exact text as granted — not AI-modified
What is claimed is:  
     
       1. A compound of the formula A:                    
       wherein: 
       R 1a , R 1b , R 1c  and R 1d  are independently selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, C 3 -C 10  cycloalkyl, R 10 O—, R 11 S(O) m —, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(O)—, CN, NO 2 , (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —,  
       c) unsubstituted or substituted C 1 -C 6  alkyl, unsubstituted or substituted C 2 -C 6  alkenyl or unsubstituted or substituted C 2 -C 6  alkynyl, wherein the substituent on the substituted C 1 -C 6  alkyl, substituted C 2 -C 6  alkenyl or substituted C 2 -C 6  alkynyl is selected from unsubstituted or substituted aryl, heterocyclic, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, R 10 O—, R 11 S(O) m —, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(O)—, CN, (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, R 10 OC(O)—, —N(R 10 ) 2 , and R 11 OC(O)—NR 10 —,  
       or two R 1a s, two R 1b s or two R 1c s, on the same carbon atom may be combined to form —(CH 2 ) t —;  
       R 2a , R 2b , R 3a  and R 3b  are independently selected from H; unsubstituted or substituted C 1-8  alkyl, unsubstituted or substituted C 2-8  alkenyl, unsubstituted or substituted C 2-8  alkynyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycle,                    
        wherein the substituted group is substituted with one or more of:  
       1) aryl or heterocycle, unsubstituted or substituted with:  
       a) C 1-4  alkyl,  
       b) (CH 2 ) p OR 6 ,  
       c) (CH 2 ) p NR 6 R 7 ,  
       d) halogen,  
       e) CN,  
       2) C 3-6  cycloalkyl,  
       3) OR 6 ,  
       4) SR 4 , S(O)R 4 , SO 2 R 4 ,  
       5) —NR 6 R 7                                        
       11) —SO 2 —NR 6 R 7                     
       15) N 3 , or  
       16) F; or  
       R 2a  and R 3a  are attached to the same carbon atom and are combined to form —(CH 2 ) u — wherein one of the carbon atoms is optionally replaced by a moiety selected from O, S(O) m , —NC(O)—, and —N(COR 10 )—; and  
       R 2a  and R 3a  are optionally attached to the same carbon atom;  
       R 4  is selected from C 1-4  alkyl, C 3-6  cycloalkyl, heterocycle, aryl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) aryl or heterocycle,  
       c) halogen,  
       d) HO,                    
       f) —SO 2 R 11 ,  
       g) N(R 10 ) 2 , or  
       h) C 1-4  perfluoroalkyl;  
       R 5 , R 6  and R 7  are independently selected from:  
       1) hydrogen,  
       2) R 10 C(O)—, or R 10 OC(O)—, and  
       3) C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 3-6  cycloalkyl, heterocycle, aryl, aroyl, heteroaroyl, arylsulfonyl, heteroarylsulfonyl, unsubstituted or substituted with one or more substituents selected from:  
       a) R 10 O—,  
       b) aryl or heterocycle,  
       c) halogen,  
       d) R 10 C(O)NR 10 —,                    
       f) —SO 2 R 11    
       g) N(R 10 ) 2 ,  
       h) C 3-6  cycloalkyl,  
       i) C 1 -C 6  perfluoroalkyl,  
       j) (R 10 ) 2 N—C(NR 10 )—,  
       k) R 10 OC(O)—,  
       l) R 11 OC(O)NR 10 —,  
       m) CN, and  
       n) NO 2 ; or  
       R 6  and R 7  may be joined in a ring; and independently,  
       R 5  and R 7  may be joined in a ring;  
       R 8  is independently selected from:  
       a) hydrogen,  
       b) unsubstituted or substituted aryl, unsubstituted or substituted heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  perfluoroalkyl, F, Cl, Br, R 12 O—, R 11 S(O) m —, R 10 C(O)NR 10 —, (R 10 ) 2 NC(O)—, R 10   2 N—C(NR 10 )—, CN, NO 2 , R 10 C(O)—, R 10 OC(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —, and  
       c) C 1 -C 6  alkyl unsubstituted or substituted by unsubstituted or substituted aryl, unsubstituted or substituted heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  perfluoroalkyl, F, Cl, Br, R 10 O—, R 11 S(O) m —, R 10 C(O)NH—, (R 10 ) 2 NC(O)—, R 10   2 N—C(NR 10 )—, CN, R 10 C(O)—, R 10 OC(O)—, —N(R 10 ) 2 , or R 10 OC(O)NH—;  
       R 9  is selected from:  
       a) hydrogen,  
       b) C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, perfluoroalkyl, F, Cl, Br, R 10 O—, R 11 S(O) m —, R 10 C(O)NR 10 —, (R 10 ) 2 NC(O)—, R 10   2 N—C(NR 10 )—, CN, NO 2 , R 10 C(O)—, R 10 OC(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —, and  
       c) C 1 -C 6  alkyl unsubstituted or substituted by C 1 -C 6  perfluoroalkyl, F, Cl, Br, R 10 O—, R 11 S(O) m —, R 10 C(O)NR 10 —, (R 10 ) 2 NC(O)—, R 10   2 N—C(NR 10 )—, CN, R 10 C(O)—, R 10 C(O)—, —N(R 10 ) 2 , or R 11  OC(O)NR 10 —;  
       R 10  is independently selected from hydrogen, C 1 -C 6  alkyl, benzyl, unsubstituted or substituted aryl and unsubstituted or substituted heterocycle;  
       R 11  is independently selected from C 1 -C 6  alkyl unsubstituted or substituted aryl and unsubstituted or substituted heterocycle;  
       R 12  is independently selected from hydrogen, C 1 -C 6  alkyl, C 1 -C 3  perfluoroalkyl, unsubstituted or substituted benzyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycle, and C 1 -C 6  alkyl substituted with unsubstituted or substituted aryl or unsubstituted or substituted heterocycle;  
       A 1  is selected from a bond, —C(O)—, —C(O)NR 10 —, —NR 10 C(O)—, O, —N(R 10 )—, —S(O) 2 N(R 10 )—, —N(R 10 )S(O) 2 —, and S(O) m ;  
       A 2  is selected from a bond, —C(O)—, —C(O)NR 10 —, —NR 10 C(O)—, O, —N(R 10 )—, —S(O) 2 N(R 10 )—, —N(R 10 )S(O) 2 —, NR 10  C(O)NR 10 —, S(O) m  and —C(R 1 c) 2 —;  
       G 1 , G 2  and G 3  are independently selected from H 2  and O;  
       W is heterocycle;  
       V is selected from:  
       a) heterocycle, and  
       b) aryl;  
       X is selected from: abond, —C(O)—, —C(O)NR 10 —, —NR 10 C(O)—, —NR 10 C(O)—O—, —O— C(O)NR 10 —, —NR 10 C(O)NR 10 —, O, —N(R 10 )—, —S(O) 2 N(R 10 )—, —N(R 10 )S(O) 2 — and S(O) m ;  
       X 1  is selected from: a bond, —C(O)—, —NR 10 C(O)—, —N(R 10 )S(O) 2 — and S(O) 2 ;  
       Y is selected from a bond, —C(═O)—, —C(O)NR 10 —, —C(O)O—, or —S(═O) m ;  
       Z 1  is selected from unsubstituted or substituted aryl and unsubstituted or substituted heterocycle, wherein the substituted aryl or substituted heterocycle is substituted with one or more of:  
       1) C 1-8  alkyl, C 2-8  alkenyl or C 2-8  alkynyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) NR 6 R 7 ,  
       c) C 3-6  cycloalkyl,  
       d) aryl or heterocycle,  
       e) HO,  
       f) —S(O) m R 4 ,  
       g) —C(O)NR 6 R 7 , or  
       h) C 1-4  perfluoroalkyl;  
       2) substituted or unsubstituted aryl or substituted or unsubstituted heterocycle,  
       3) halogen,  
       4) OR 6 ,  
       5) NR 6 R 7 ,  
       6) CN,  
       7) NO 2 ,  
       8) CF 3 ;  
       9) —S(O) m R 4 ,  
       10) —OS(O) 2 R 4 ,  
       11) —C(O)NR 6 R 7 ,  
       12) —C(O)OR 6 , or  
       13) C 3 -C 6  cycloalkyl;  
       Z 2  is selected from a bond, unsubstituted or substituted aryl and unsubstituted or substituted heterocycle, wherein the substituted aryl or substituted heterocycle is substituted with one or more of:  
       1) C 1-8  alkyl, C 2-8  alkenyl or C 2-8  alkynyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) NR 6 R 7 ,  
       c) C 3-6  cycloalkyl,  
       d) aryl or heterocycle,  
       e) HO,  
       f) —S(O) m R 4 ,  
       g) —C(O)NR 6 R 7 , or  
       h) C 1-4  perfluoroalkyl;  
       2) substituted or unsubstituted aryl or substituted or unsubstituted heterocycle,  
       3) halogen,  
       4) OR 6 ,  
       5) NR 6 R 7 ,  
       6) CN,  
       7) NO 2 ,  
       8) CF 3 ,  
       9) —S(O) m R 4 ,  
       10) —OS(O) 2 R 4 ,  
       11) —C(O)NR 6 R 7 ,  
       12) —C(O)OR 6 , or  
       13) C 3 -C 6  cycloalkyl;  
       m is 0, 1 or 2;  
       n is 0, 1, 2, 3 or 4;  
       p is independently 0, 1, 2, 3 or 4;  
       q is 1 or 2;  
       r is 0 to 5;  
       s is independently 0, 1, 2 or 3;  
       t is 2, 3, 4, 5 or 6; and  
       u is 4 or 5;  
       or a pharmaceutically acceptable salt or stereoisomer thereof. 
     
     
       2. The compound according to  claim 1  of the formula B:                    
       wherein: 
       R 1a , R 1b  and R 1c  is independently selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, C 3 -C 10  cycloalkyl, R 10 O—, —N(R 10 ) 2  or C 2 -C 6  alkenyl, and  
       c) C 1 -C 6  alkyl unsubstituted or substituted by aryl, heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, R 10 O—, or —N(R 10 ) 2 ;  
       R 1d  is selected from:  
       a) hydrogen,  
       b) unsubstituted or substituted aryl, unsubstituted or substituted heterocycle, C 3 -C 10  cycloalkyl, R 10 O—, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(O) NR 10 —, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —,  
       c) unsubstituted or substituted C 1 -C 6  alkyl, unsubstituted or substituted C 2 -C 6  alkenyl or unsubstituted or substituted C 2 -C 6  alkynyl, wherein the substituent on the substituted C 1 -C 6  alkyl, substituted C 2 -C 6  alkenyl or substituted C 2 -C 6  alkynyl is selected from unsubstituted or substituted aryl, heterocyclic, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  perfluoroalkyl, halogen, R 10 O—, R 4 S(O) m —, R 4 S(O) 2 NR 10 —, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(O)—, CN, (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, R 10 OC(O)—, —N(R 10 ) 2 , and R 11 OC(O)—NR 10 —;  
       R 3a  is selected from H and CH 3 ;  
       R 2a  is selected from H;                    
       and C 1-5  alkyl, unbranched or branched, unsubstituted or substituted with one or more of:  
       1) aryl,  
       2) heterocycle,  
       3) OR 6 ,  
       4) SR 4 , SO 2 R 4 , or                    
       and any two of R 2a  and R 3a  are optionally attached to the same carbon atom;  
       R 4  is selected from:  
       C 1-4  alkyl and C 3-6  cycloalkyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) halogen, or  
       c) aryl or heterocycle;  
       R 6  and R 7  are independently selected from H; C 1-6  alkyl, C 3-6  cycloalkyl, heterocycle, aryl, aroyl, heteroaroyl, arylsulfonyl, heteroarylsulfonyl, unsubstituted or substituted with one or two:  
       a) C 1-4  alkoxy,  
       b) aryl or heterocycle,  
       c) halogen,  
       d) HO,                    
       f) —SO 2 R 11 ,  
       g) N(R 10 ) 2 , or  
       h) C 3-6  cycloalkyl;  
       R 8  is independently selected from:  
       a) hydrogen,  
       b) unsubstituted or substituted aryl, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  perfluoroalkyl, F, Cl, R 12 O—, R 10 C(O)NR 10 —, CN, NO 2 , (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —, and  
       c) C 1 -C 6  alkyl substituted by: unsubstituted or substituted aryl, C 1 -C 6  perfluoroalkyl, R 10 O—, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —;  
       R 9a  is selected from hydrogen, C 1 -C 6  alkyl and C 1 -C 6  perfluoroalkyl;  
       R 10  is independently selected from hydrogen, C 1 -C 6  alkyl, benzyl and unsubstituted or substituted aryl;  
       R 11  is independently selected from C 1 -C 6  alkyl and unsubstituted or substituted aryl;  
       R 12  is independently selected from hydrogen, C 1 -C 6  alkyl, unsubstituted or substituted benzyl, unsubstituted or substituted aryl, unsubstituted or substituted heterocycle, and C 1 -C 6  alkyl substituted with unsubstituted or substituted aryl or unsubstituted or substituted heterocycle;  
       A 1  is selected from a bond, —N(R 10 )—, S(O) m  and O;  
       G 1 , G 2  and G 3  are independently selected from H 2  and O;  
       V is selected from:  
       a) heterocycle selected from pyridinyl, pyridonyl, 2-oxopiperidinyl, indolyl, quinolinyl and isoquinolinyl, and  
       b) aryl;  
       X is selected from a bond, —C(═O)—, —NR 10 C(O)—, —OC(O)— or —S(═O) m ;  
       Y is selected from a bond, —C(═O)—, —C(O)NR 10 —, —C(O)O—, or —S(═O) m ;  
       Z 1  is selected from unsubstituted or substituted aryl or unsubstituted or substituted heterocycle, wherein the substituted aryl or substituted heterocycle is independently substituted with one or two of:  
       1) C 1-8  alkyl, C 2-8  alkenyl or C 2-8  alkynyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) NR 6 R 7 ,  
       c) C 3-6  cycloalkyl,  
       d) aryl or heterocycle,  
       e) HO,  
       f) —S(O) m R 4 ,  
       g) —C(O)NR 6 R 7 , or  
       h) C 1-4  perfluoroalkyl;  
       2) substituted or unsubstituted aryl or substituted or unsubstituted heterocycle,  
       3) halogen,  
       4) OR 6 ,  
       5) NR 6 R 7 ,  
       6) CN,  
       7) NO 2 ,  
       8) CF 3 ,  
       9) —S(O) m R 4 ,  
       10) —OS(O) 2 R 4 ,  
       11) —C(O)NR 6 R 7 ,  
       12) —C(O)OR 6 , or  
       13) C 3 -C 6  cycloalkyl;  
       m is 0, 1 or 2;  
       n is 0, 1, 2, 3 or 4;  
       p is 0, 1, 2, 3 or 4;  
       r is 0 to 5; and  
       s is independently 0, 1, 2 or 3;  
       or a pharmaceutically acceptable salt or stereoisomer thereof. 
     
     
       3. The compound according to  claim 2  of the formula C:                    
       wherein: 
       R 1a , R 1b  and R 1c  is independently selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, C 3 -C 10  cycloalkyl, R 10 O—, —N(R 10 ) 2  or C 2 -C 6  alkenyl, and  
       c) C 1 -C 6  alkyl unsubstituted or substituted by aryl, heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, R 10 O—, or —N(R 10 ) 2 ;  
       R 1d  is selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, C 3 -C 10  cycloalkyl, R 10 O—, —N(R 10 ) 2  or C 2 -C 6  alkenyl, and  
       c) C 1 -C 6  alkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, unsubstituted or substituted by aryl, heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, R 10 O—, or —N(R 10 ) 2 ;  
       R 3a  is selected from H and CH 3 ;  
       R 2a  is selected from H;                    
       and C 1-5  alkyl, unbranched or branched, unsubstituted or substituted with one or more of:  
       1) aryl,  
       2) heterocycle,  
       3) OR 6 ,  
       4) SR 4 , SO 2 R 4 , or                    
       and any two of R 2a  and R 3a  are optionally attached to the same carbon atom;  
       R 4  is selected from C 1-4  alkyl and C 3-6  cycloalkyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) halogen, or  
       c) aryl or heterocycle;  
       R 6  and R 7  are independently selected from:  
       a) hydrogen,  
       b) C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, R 10 C(O)— or R 10 OC(O)— and  
       c) C 1 -C 6  alkyl substituted by C 1 -C 6  perfluoroalkyl, R 10 O—, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, R 10 OC(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —;  
       R 8  is independently selected from:  
       a) hydrogen,  
       b) unsubstituted or substituted aryl, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  perfluoroalkyl, F, Cl, R 12 O—, R 10 C(O)NR 10 —, CN, NO 2 , (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —, and  
       c) C 1 -C 6  alkyl substituted by unsubstituted or substituted aryl, C 1 -C 6  perfluoroalkyl, R 10 —, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —;  
       R 9a  is selected from hydrogen, C 1 -C 6  alkyl and C 1 -C 6  perfluoroalkyl;  
       R 10  and R 12  are independently selected from hydrogen, C 1 -C 6  alkyl, benzyl and unsubstituted or substituted aryl;  
       R 11  is independently selected from C 1 -C 6  alkyl and unsubstituted or substituted aryl;  
       A 1  is selected from a bond, —N(R 10 )—, S(O) m  and O;  
       X is selected from a bond, —C(═O)—, —NR 10 C(O)—, —OC(O)— or —S(═O) m ;  
       Y is selected from a bond, —C(═O)—, —C(O)NR 10 —, —C(O)O—, or —S(═O) m ;  
       Z 1  is selected from unsubstituted or substituted aryl or unsubstituted or substituted heterocycle, wherein the substituted aryl or substituted heterocycle is substituted with one or two of:  
       1) C 1-4  alkyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) NR 6 R 7 ,  
       c) C 3-6  cycloalkyl,  
       d) aryl or heterocycle,  
       e) HO,  
       f) —S(O) m R 4 , or  
       g) —C(O)NR 6 R 7 ,  
       2) aryl or heterocycle,  
       3) halogen,  
       4) OR 6 ,  
       5) NR 6 R 7 ,  
       6) CN,  
       7) NO 2 ,  
       8) CF 3 ,  
       9) —S(O) m R 4 ,  
       10) —C(O)NR 6 R 7 , or  
       11) C 3 -C 6  cycloalkyl;  
       m is 0, 1 or 2;  
       n is 0, 1, 2, 3 or 4;  
       p is 0, 1, 2, 3 or 4;  
       r is 0 to 5; and  
       s is independently 0, 1, 2 or 3 ;  
       or a pharmaceutically acceptable salt or stereoisomer thereof. 
     
     
       4. The compound according to  claim 3  of the formula D:                    
       wherein: 
       R 1b  and R 1c  is independently selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, C 3 -C 10  cycloalkyl, R 10 O— —N(R 10 ) 2 , and  
       c) C 1 -C 6  alkyl unsubstituted or substituted by aryl, heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, R 10 O—, or —N(R 10 ) 2 ;  
       R 1d  is selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, C 3 -C 10  cycloalkyl, R 10 O— or —N(R 10 ) 2 , and  
       c) C 1 -C 6  alkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, unsubstituted or substituted by aryl, heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, R 10 O—, or —N(R 10 ) 2 ;  
       R 3a  is selected from H and CH 3 ;  
       R 2a  is selected from H;                    
       and C 1-5  alkyl, unbranched or branched, unsubstituted or substituted with one or more of:  
       1) aryl,  
       2) heterocycle,  
       3) OR 6 ,  
       4) SR 4 , SO 2 R 4 , or                    
       and any two of R 2  and R 3  are optionally attached to the same carbon atom;  
       R 4  is selected from C 1-4  alkyl and C 3-6  cycloalkyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) halogen, or  
       c) aryl or heterocycle;  
       R 6  and R 7  are independently selected from H; C 1-6  alkyl, C 3-6  cycloalkyl, aryl, aroyl, arylsulfonyl, unsubstituted or substituted with one or two:  
       a) C 1-4  alkoxy,  
       b) aryl,  
       c) halogen,  
       d) HO,                    
       f) —SO 2 R 11 ,  
       g) N(R 10 ) 2 ,  
       h) C 3-6  cycloalkyl; or  
       R 8  is independently selected from:  
       a) hydrogen,  
       b) unsubstituted or substituted aryl, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  perfluoroalkyl, F, Cl, R 12 O—, R 10 C(O)NR 10 —, CN, NO 2 , (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —, and  
       c) C 1 -C 6  alkyl substituted by unsubstituted or substituted aryl, C 1 -C 6  perfluoroalkyl, R 10 O—, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —;  
       R 9a  is selected from hydrogen, C 1 -C 6  alkyl and C 1 -C 6  perfluoroalkyl;  
       R 10  and R 12  are independently selected from hydrogen, C 1 -C 6  alkyl, benzyl and unsubstituted or substituted aryl;  
       R 11  is independently selected from C 1 -C 6  alkyl and unsubstituted or substituted aryl;  
       A 11  is selected from a bond, —N(R 10 )—, S(O) m  and O;  
       X is selected from a bond, —C(═O)—, —NR 10  OC(O)—, —OC(O)— or —(═O) m ;  
       Y is selected from a bond, —C(═O)—, —C(O)NR 10 —, —C(O)O—, or —S(═O) m ;  
       Z 1  is selected from unsubstituted or substituted aryl or unsubstituted or substituted heterocycle, wherein the substituted aryl or substituted heterocycle is substituted with one or two of:  
       1) C 1-8  alkyl, C 2-8  alkenyl or C 2   8  alkynyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) NR 6 R 7 ,  
       c) C 3-6  cycloalkyl,  
       d) aryl or heterocycle,  
       e) HO,  
       f) —S(O) m R 4 ,  
       g) —C(O)NR 6 R 7 , or  
       h) C 1-4  perfluoroalkyl;  
       2) substituted or unsubstituted aryl or substituted or unsubstituted heterocycle,  
       3) halogen,  
       4) OR 6 ,  
       5) NR 6 R 7 ,  
       6) CN,  
       7) NO 2 ,  
       8) CF 3 ,  
       9) —S(O) m R 4 ,  
       10) —OS(O) 2 R 4 ,  
       11) —C(O)NR 6 R 7 ,  
       12) —C(O)OR 6 , or  
       13) C 3 -C 6  cycloalkyl;  
       m is 0, 1 or 2;  
       p is independently 0, 1, 2, 3 or 4;  
       r is 0 to 5; and  
       s is independently 0, 1, 2 or 3;  
       or a pharmaceutically acceptable salt or stereoisomer thereof. 
     
     
       5. The compound according to  claim 3  of the formula E:                    
       wherein: 
       R 1b  and R 1c  is independently selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, cycloalkyl, R 10 O—, —N(R 10 ) 2  or C 2 -C 6  alkenyl, and  
       c) C 1 -C 6  alkyl unsubstituted or substituted by aryl, heterocycle, cycloalkyl, alkenyl, R 10 O—, or —N(R 10 ) 2 ;  
       R 1d  is selected from:  
       a) hydrogen,  
       b) aryl, heterocycle, C 3 -C 10  cycloalkyl or C 2 -C 6  alkenyl, and  
       c) C 1 -C 6  alkyl, C 2 -C 6  alkenyl or C 2 -C 6  alkynyl, unsubstituted or substituted by aryl, heterocycle, C 3 -C 10  cycloalkyl, C 2 -C 6  alkenyl, R 10 O—, or —N(R 10 ) 2 ;  
       R 3a  is selected from H and CH 3 ;  
       R 2a  is selected from H;                    
       and C 1-5  alkyl, unbranched or branched, unsubstituted or substituted with one or more of:  
       1) aryl,  
       2) heterocycle,  
       3) OR 6 ,  
       4) SR 4 , SO 2 R 4 , or                    
       and any two of R 2a  and R 3a  are optionally attached to the same carbon atom;  
       R 4  is selected from C 1-4  alkyl and C 3-6  cycloalkyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) fluoro, or  
       c) aryl or heterocycle;  
       R 6  and R 7  are independently selected from H; C 1-6  alkyl, C 3-6  cycloalkyl, aryl, aroyl, arylsulfonyl, unsubstituted or substituted with one or two:  
       a) C 1-4  alkoxy,  
       b) aryl,  
       c) halogen,  
       d) HO,                    
       f) —SO 2 R 11 ,  
       g) N(R 10 ) 2 , or  
       h) C 3-6  cycloalkyl,  
       R 8  is independently selected from:  
       a) hydrogen,  
       b) unsubstituted or substituted aryl, C 1 -C 6  alkyl, C 2 -C 6  alkenyl, C 2 -C 6  alkynyl, C 1 -C 6  perfluoroalkyl, F, Cl, R 12 O—, R 10 C(O)NR 10 —, CN, NO 2 , (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —, and  
       c) C 1 -C 6  alkyl substituted by unsubstituted or substituted aryl, C 1 -C 6  perfluoroalkyl, R 10 O—, R 10 C(O)NR 10 —, (R 10 ) 2 N—C(NR 10 )—, R 10 C(O)—, —N(R 10 ) 2 , or R 11 OC(O)NR 10 —;  
       R 9a  is selected from hydrogen, C 1 -C 6  alkyl and C 1 -C 6  perfluoroalkyl;  
       R 10  and R 12  are independently selected from hydrogen, C 1 -C 6  alkyl, benzyl and unsubstituted or substituted aryl;  
       R 11  is independently selected from C 1 -C 6  alkyl and unsubstituted or substituted aryl;  
       A 1  is selected from a bond, —N(R 10 )—, S(O) m  and O;  
       X is selected from a bond, —C(═O)—, —NR 10 C(O)—, —OC(O)— or —S(═O) m ;  
       Y is selected from a bond, —C(═O)—, —C(O)NR 10 —, —C(O)O—, or —S(═O) m ;  
       Z 1  is selected from unsubstituted or substituted aryl or unsubstituted or substituted heterocycle, wherein the substituted aryl or substituted heterocycle is substituted with one or two of:  
       1) C 1-8  alkyl, C 2-8  alkenyl or C 2-8  alkynyl, unsubstituted or substituted with:  
       a) C 1-4  alkoxy,  
       b) NR 6 R 7 ,  
       C) C 3-6  cycloalkyl,  
       d) aryl or heterocycle,  
       e) HO,  
       f) —S(O) m R 4 ,  
       g) —C(O)NR 6 R 7 , or  
       h) C 1-4  perfluoroalkyl;  
       2) substituted or unsubstituted aryl or substituted or unsubstituted heterocycle,  
       3) halogen,  
       4) OR 6 ,  
       5) NR 6 R 7 ,  
       6) CN,  
       7) NO 2 ,  
       8) CF 3 ,  
       9) —S(O) m R 4 ,  
       10) —OS(O) 2 R 4 ,  
       11) —C(O)NR 6 R 7 ,  
       12) —C(O)OR 6 , or  
       13) C 3 -C 6  cycloalkyl;  
       m is 0, 1 or 2;  
       p is independently 1, 2, 3 or 4;  
       r is 0 to 5; and  
       s is independently 0, 1, 2 or 3;  
       or a pharmaceutically acceptable salt or stereoisomer thereof. 
     
     
       6. A compound which is selected from: 
       14-amino-14-(1-methyl-1H-imidazol-5-yl)-8-oxa-2-thia-1,18-diazatetracyclo[16.2.2.1 3,7 .1 9,13 ]tetracosa-3(24),4,6,9(23),10,12-hexaene-10-carbonitrile 2,2-dioxide;  
       14-amino-4-chloro-14-(1-methyl-1H-imidazol-5-yl)—20-oxo-8-oxa-1,18-diazatetracyclo[16.2.2.1 3,7 .1 9,13 ]tetracosa-3(24),4,6,9(23),10,12-hexaene-10-carbonitrile;  
       18-Bromo-8-[5-(1-methyl-1H-imidazolyl)]-8-methyl-3,7:1,17-dimetheno-11H-10,14-dioxo-12,15-ethano-16H-2-oxa-9,10:13,14-tetrahydro-[9,12,15]triaza-cycloeicosene-4-carbonitrile;  
       18-Chloro-8-[5-(1-methyl-1H-imidazolyl)]-8-methyl-3,7:1,17-dimetheno-11H-10,14-dioxo-12,15-ethano-16H-2-oxa-9,10:13,14-tetrahydro-[9,12,15]triaza-cycloeicosene-4-carbonitrile;  
       or a pharmaceutically acceptable salt or stereoisomer thereof. 
     
     
       7. The compound according to  claim 6  which is 
       14-amino-14-(1-methyl-1H-imidazol-5-yl)-8-oxa-2-thia-1,18-diazatetracyclo[16.2.2.1 3,7 .1 9,13 ]tetracosa-3(24),4,6,9(23),10,12-hexaene-10-carbonitrile 2,2-dioxide                    
       or a pharmaceutically acceptable salt or stereoisomer thereof. 
     
     
       8. A pharmaceutical composition comprising a pharmaceutical carrier, and dispersed therein, a therapeutically effective amount of a compound of  claim 1 . 
     
     
       9. A pharmaceutical composition comprising a pharmaceutical carrier, and dispersed therein, a therapeutically effective amount of a compound of  claim 3 . 
     
     
       10. A pharmaceutical composition comprising a pharmaceutical carrier, and dispersed therein, a therapeutically effective amount of a compound of  claim 6 . 
     
     
       11. A method for treating blindness related to retinal vascularization which comprises administering to a mammal in need thereof a therapeutically effective amount of a composition of  claim 8 . 
     
     
       12. A method for treating infections from hepatitis delta which comprises administering to a mammal in need thereof a therapeutically effective amount of a composition of  claim 8 . 
     
     
       13. A method for preventing restenosis after percutaneous transluminal coronary angioplasty which comprises administering to a mammal in need thereof a therapeutically effective amount of a composition of  claim 8 . 
     
     
       14. A method for treating polycystic kidney disease which comprises administering to a mammal in need thereof a therapeutically effective amount of a composition of  claim 8 . 
     
     
       15. A method of conferring radiation sensitivity on a tumor cell using a therapeutically effective amount of a composition of  claim 8  in combination with radiation therapy. 
     
     
       16. A method of using a therapeutically effective amount of a composition of  claim 8  in combination with an antineoplastic to treat cancer. 
     
     
       17. A method according to  claim 16  wherein the antineoplastic is paclitaxel. 
     
     
       18. A process for making a pharmaceutical composition comprising combining a compound of  claim 1  and a pharmaceutically acceptable carrier.

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